There's lots of little breaks though with double-spaces to indicate shifts in scene. But formal chapters, not so much. I seem to recall actual chapter breaks within The Tiffany Aching books, especially Wintersmith and I Shall Wear Midnight.

I love Discworld. I'm so happy to still have another 23+ books to read in the series.

Q: You've said that as "life doesn't happen in chapters," you don't use them in your books. What was different about Going Postal?

A: I have to use chapters in children's books! Apparently it's so mum & dad when they are reading to the child can say "I'll read to the end of the chapter then you have to go to sleep." Going Postal, and indeed it's successor making Money both have a somewhat Victorian feel to them so I thought it might be fun to go back to the glorious era of chapter headings which were practically an index to the book! In the same way I found you could have fun with footnotes, I have now learned that chapter headings can be quite amusing.

I've been wanting to try the Discworld books for years, but geesh, there's so many! I wouldn't know where to begin.

As jgaiser wrote, you could pick up any book just to see how you like the style.
The first Discworld book I read was "The Fifth Elephant".

I'm sure each fan of the Discworld books have their own favourite(s) (if I'd be pushed to chose just 1 book it would probably be "The Night Watch") but I would recommend you start with "Guards! Guards!" and go on from there with the whole "Watch" series.

For me "The Watch" series is way above the other ones.
After this comes the "Witches" series.
Special mention outside of the "Watch" series would be for "Thief of Time", "The Truth" and especially "The Monstrous Regiment".

Small Gods is also a very good standalone novel.
But personally I think it best to start with the first and go on from there (publishing order), how else are you supposed to decide which ones you like best?